1 SUPPLEMENTARY ONLINE MATERIAL:
2 Analytical conditions for GC-MRM-MS and GC-QQQ-MS:
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The Waters Micromass Autospec Ultima was equipped with an Agilent 6890N gas chromatograph and a J&W Scientific DB-5 fused silica capillary column (60 m x 0.25 mm i.d., 0.25 μm film thickness) using He as carrier gas. The GC oven was ramped from
60°C (1 min.) to 155°C at 15°C /min and then to 325°C at 4°C/min, finally holding for
25.20 min. Samples were injected in splitless mode into a PTV injector at 330°C. The perfluorokerosene (PFK) tune file was modified to include a lower magnet mass from an air peak in order to improve analysis of the intact C
40
carotenoid carbon skeletons.
The MS source was operated in EI-mode at 250°C with an ionization energy of 70 eV and an 8 kV acceleration voltage. The molecular ion to fragment ion transitions were acquired as two consecutive functions. The first function comprised transitions corresponding to the C
14
-
25
aryl isoprenoids, and the second function monitored 13 transitions including the C
40
carotenoid transitions, which had a total cycle time of
819.76 ms. Due to the different intensities of the m/z 133/134 base peak intensities, the
546 => 134 transition is enhanced for paleorenieratane relative to isorenieratane. With the exception of paleorenieratane and γ-carotane, compound identification for the
MRM analysis was confirmed by co-elution experiments with synthetic standards and a rock extract from the BCF (Brocks et al., 2005). The identification of paleorenieratane for
MRM analysis was confirmed by co-elution experiments with a Devonian sample,
Blina-1, from Western Australia containing paleorenieratane and by comparison of a full scan mass spectrum with published mass spectra (Requejo et al., 1992).
The GC-QQQ-MS was operated in multiple reaction monitoring mode using an
Agilent 7000A Triple Quad equipped with an Agilent 7890A gas chromatograph and a
J&W Scientific DB-5MS+DG fused capillary column (60 m x 0.25 mm i.d., 0.25 μm film thickness, 10 m guard column) using He as carrier gas. The GC oven was ramped from
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40°C (2 min.) to 325°C at 4°C /min, holding for 25.75 min. The carrier flow was ramped from 1.2 mL/ min. (0 min.) to 3.2 mL /min. Samples were injected in cold splitless mode at 45°C and the injector was ramped at 700°C /min to 300°C. The MS source was operated in EI-mode at 300°C with an ionization energy of -70 eV. The number of molecular ion to fragment transitions varied throughout the run; dwell time was adjusted as needed to produce 3.5 cycles/second. MS1 & MS2 resolution was set to
“widest”. The collision energy for β-carotane and γ-carotane was 5 eV, and it was 3 eV for chlorobactane, okenane, paleorenieratane & isorenieratane. Identification of all carotenoids was achieved by comparison of mass spectra and relative retention times to published data derived from full scan GC-MS.
A dilution series of synthetic standards were analyzed by GC-MRM-MS to estimate a limit of detection. An aliquot of β-carotene was catalytically hydrogenated to
28.6 mg of β-carotane using PtO
2
, hexane, and acetic acid while continuously stirring and bubbling H
2 (g)
. The purity of the hydrogenation product was tested by GC, and after GC-purity was achieved, a set of β-carotane standards of known concentrations was prepared. The concentrations of the isorenieratane and chlorobactane synthetic standards (courtesy of P Schaeffer) were determined by comparison of the gas chromatography/ flame ionization detection (GC-FID) peak area to the GC-FID peak area of a β-carotane standard of known concentration. GC-MRM-MS analysis of a dilution series of β-carotane, isorenieratane, and chlorobactane standards indicates that saturated C
40
carotanes, diaromatic C
40
carotenoids, and monoaromatic C
40
carotenoids can be detected to concentrations as low as ~10 pg.
CONSTRUCTION OF STRATIGRAPHIC DISTRIBUTION PLOT
Earlier compilations of aromatic carotenoid derivatives in ancient depositional systems was updated and modified to only include isorenieratane, chlorobactane, paleorenieratane, and okenane in marine environments (Sinninghe Damsté and
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Schouten, 2006; Meyer and Kump, 2008). The unsaturated precursors were included in addition to the hydrogenated diagenetic products so occurrences of aromatic C
40 carotenoids in geologically young or modern marine samples were not neglected. Table
S1 includes the references used to build figure 4A. During some intervals, particularly
Mesozoic OAEs, there are many reports of carotenoid detection, but in order to avoid redundancy, table S1 only lists the most comprehensive references for a given time interval, emphasizing the earliest references where possible.
The geologic time scale was scaled vertically, but the vertical time scale was multiplied by a factor of 6.25 in the Precambrian compared to the Phanerozoic. A published report of a C
40
carotenoid was treated equally as single band of constant thickness because age control was rarely good enough to determine the precise duration of carotenoid occurrence. A slightly thicker band was used to represent the new tandem mass spectrometry results in figure 4B. A dashed vertical line was used to denote age uncertainty for some of the oils analyzed for this study where the uncertainty was greater than the band thickness. Table 1 lists the sample information for the samples analyzed by tandem mass spectrometry for this study. The detection of isorenieratane, chlorobactane, paleorenieratane, and/or okenane in these samples was recorded in
Table 1. Samples containing chlorobactane, okenane, and/or paleorenieratane always contained additional carotenoids, such as isorenieratane, renieratane, renierapurpurane,
β-isorenieratane, β-renierapurpurane, β-carotane, and/or γ-carotane. However, a band representing the new results was placed into figure 4B only if that specific carotenoid had not been reported in the literature during that time interval.
3

Table S1. Literature References for Construction of Figure 4A
Age
Aromatic C
40
Carotenoid*
Locality
Holocene
Holocene
Holocene
Pliocene
Messinian
Messinian
Oligocene
ETM-2
PETM
OAE-3
Late Turonian
OAE-2
OAE-1b
OAE-1a
Late Jurassic
Late Jurassic
Middle Callovian
Toarcian
Toarcian OAE
Middle Sinemurian to Middle
Hettangian
1
1
1
1
1, 2
1
1, 2
1
1
1
1, 2
1
1, 2
1, 4
1
1, 2
1
1, 2
1, 2, 4
1
References
Black Sea
Amvrakikos Gulf (Greece)
Kyllaren Fjord
Eastern Mediterranean Sapropels (ODP)
Vena del Gesso Basin (Italy)
Gebellina Marl (Sicily)
Menilite Formation (Poland)
Arctic Ocean (IODP)
Arctic Ocean (IODP)
Deep Ivorian Basin (ODP)
Canje Formation (British Guyana)
North Atlantic (DSDP & ODP)
Santana Formation (Brazil)
Venetian Alps (Italy)
Kimmeridge Clay (UK)
Calcaires en Plaquettes (France)
Oxford Clay (UK)
Northern Europe (Allgäu; Schistes Cartons;
Posidionia)
Hawsker Bottoms; Cleveland Basin UK; MRM rock extract
Frick Swiss Jura
(Repeta et al., 1989; Repeta, 1993)
(Naeher et al., 2012)
(Smittenberg et al., 2004)
(Passier et al., 1999)
(Kohnen et al., 1992)
(Schaeffer et al., 1995)
(Koopmans et al., 1996)
(Sluijs et al., 2009)
(Sluijs et al., 2006)
(Wagner et al., 2004)
(Koopmans et al., 1996)
(Kuypers et al., 2002; van Bentum et al., 2009)
(Heimhofer et al., 2008)
(van Breugel et al., 2007)
(Koopmans et al., 1996)
(Koopmans et al., 1996; Van Kaam-Peters and
Sinninghe Damsté, 1997)
(Koopmans et al., 1996)
(Koopmans et al., 1996; Schouten et al., 2000)
(French et al., 2014)
(Schwab and Spangenberg, 2007)
4

Upper Hettangian
Norian-Rhaetian
Norian
Early–Mid Triassic; Olenekian–
Anisian
Early Triassic
Early Triassic
Early Triassic to Late Permian
Late Permian
1
1
1
2, 4
1
1, 2
1, 2
1
1
1, 3
1, 3
1, 3
Northern Europe
Kössen Marl (Hungary)
Hauptdolomit (Germany)
Chaohu sections, South China
Perth Basin (Australia)
Peace River (Canada)
Meishan (China)
Kupferschiefer (Germany)
Minnelusa Formation (USA)
Exshaw Formation (Canada)
Holy Cross Mountains (Poland)
Holy Cross Mountains (Poland)
(Richoz et al., 2012)
(Koopmans et al., 1996)
(Koopmans et al., 1996)
(Saito et al., 2014)
(Grice et al., 2005)
(Hays, 2010)
(Cao et al., 2009; Hays, 2010)
(Schwark and Püttmann, 1990; Grice et al.,
1996)
(Koopmans et al., 1996) Late Carboniferous
Early Carboniferous
Upper Famennian
Frasnian/Famennian
Frasnain 1, 3
1
1
1, 3
1, 3
1, 3
1, 3
1
1, 3
Duvernay Fm (Canada)
Holy Cross Mountains (Poland)
Keg River Formation (Canada)
Batra Formation (Jordon)
Boas Oil Shale (Canada)
Decorah Formation (USA)
Womble Shale (USA)
Hagen Member (Australia)
Arthur Creek Formation (Australia)
(Koopmans et al., 1996)
(Racka et al., 2010)
(Joachimski et al., 2001)
(Requejo et al., 1992; Hartgers et al., 1993;
Hartgers et al., 1994)
(Marynowski et al., 2008) Early–Mid Frasnian transition
Middle Devonian; Givetian
Late Ordovician–Early Silurian
Late Ordovician
Caradocian
Middle Ordovician
Late Cambrian
Middle Cambrian
Middle Cambrian 1 Thorntonia Limestone (Australia)
(Behrens et al., 1998)
(Armstrong et al., 2009)
(Koopmans et al., 1996)
(Pancost et al., 1998)
(Koopmans et al., 1996)
(Boreham and Ambrose, 2005)
(Boreham and Ambrose, 2005)
(Boreham and Ambrose, 2005)
Late Paleoproterozoic 1, 2, 4 Barney Creek Formation (Australia) (Brocks et al., 2005)
* Isorenieratane and Isorenieratene are designated by 1 . Chlorobactane or Chlorobactene are designated by 2 . Paleorenieratane is designated by 3 . Okenane or
Okenone are designated by 4 .
5

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